1. Excitons – Types, Energy Transfer
•Wannier exciton
•Charge-transfer exciton
•Frenkel exciton
•Exciton Diffusion
•Exciton Energy Transfer (Förster, Dexter)
Handout (for Recitation Discusssion):
J.-S. Yang and T.M. Swager, J. Am. Chem. Soc. 120, 5321 (1998)
Q. Zhou and T.M. Swager, J. Am. Chem. Soc. 117, (1995)
@ MIT
February 27, 2003 – Organic Optoelectronics - Lecture 7

2. Exciton
In some applications it is useful to consider electronic excitation as if a
quasi-principle, capable of migrating, were involved. This is termed as
exciton. In organic materials two models are used: the band or wave model
(low temperature, high crystalline order) and the hopping model (higher
temperature, low crystalline order or amorphous state). Energy transfer in
the hopping limit is identical with energy migration.
Caption from IUPAC Compendium of Chemical Terminology
compiled by Alan D. McNaught and Andrew Wilkinson
(Royal Society of Chemistry, Cambridge, UK).

3. Excitons (bound electron-hole pairs) Wannier exciton
(typical of inorganic
semiconductors)
Frenkel exciton
(typical of organic
materials)
treat excitons
as chargeless
particles
capable of
diffusion,
also view
them as
excited states
of the
molecule
MOLECULAR PICTURE
SEMICONDUCTOR PICTURE
Charge Transfer (CT)
Exciton
(typical of organic
materials)
GROUND STATE FRENKEL EXCITON
GROUND STATE WANNIER EXCITON
binding energy ~10meV
radius ~100Å
binding energy ~1eV
radius ~10Å
Electronic Processes in Organic Crystals and Polymers by M. Pope and C.E. Swenberg

4. Wannier-Mott Excitons
Columbic interaction between
the hole and the electron is given by
EEX = -e2/∈r
The exciton energy is then
E = EION – EEX/n2 , n = 1,2, …
EION – energy required to ionize the molecule
n – exciton energy level
EEX = 13.6 eV μ/m∈
μ– reduced mass =memh / (me+mh)
Adapted from Electronic Processes in Organic Crystals and Polymers by M. Pope and C.E. Swenberg

5. An Example of Wannier-Mott Excitons
exciton progression
fits the expression
ν[cm-1] = 17,508 – 800/n2
corresponding to
μ = 0.7 and ∈ = 10
The absorption spectrum of Cu2O
at 77 K, showing the exciton lines
corresponding to several values
of the quantum number n. (From
Baumeister 1961).
Quoted from Figure I.D.28.
Electronic Processes in Organic
Crystals and Polymers by M. Pope
and C.E. Swenberg

6. Charge Transfer Excitons
The lowest CT exciton state
in the ab plane of an
anthracene crystal with two
inequivalent molecules per
unit cell; the plus and minus
signs refer to the center of
gravity of charge distribution.
The Frenkel exciton obtains
when both (+) and (–) occupy
essentially the same
molecular site.

7. Crystalline Organic Films
CHARGED CARRIER MOBILITY
INCREASES WITH INCREASED
π−π ORBITAL OVERLAP
GOOD CARRIER MOBILITY
IN THE STACKING DIRECTION
μ = 0.1 cm2/Vs – stacking direction
μ = 10-5 cm2/Vs – in-plane direction
Highest mobilities obtained on
single crystal
pentacene μ = 10 5 cm2/Vs at 10K
tetracene μ = 10 4 cm2/Vs at 10K
(Schön, et al., Science 2000).

8. PTCDA monolayer on HOPG
Organic Semiconducting Materials
Van der Waals-BONDED
ORGANIC CRYSTALS
(and amorphous films)
PTCDA monolayer on HOPG
(STM scan)
HOMO of
3,4,9,10- perylene tetracarboxylic dianhydride

9. PTCDA Solution (~ 2μM in DMSO)

10. PTCDA Thin Film

11. PTCDA Solution
PTCDA Thin Film
(~ 2μM in DMSO)
(~ 2μM in DMSO)

12. Solution Absorption

13. Absorption of Vibronic Transitions
– Change with Solution Concentration

14. Solution Luminescence

15. Monomer and Aggregate Concentration in Solution

16. PTCDA Electron Energy Structure
Absorption
Luminescence

17. PTCDA Solution
PTCDA Thin Film
(~ 2μM in DMSO)
(~ 2μM in DMSO)

18. Solution and Thin Film Fluorescence
fluorescence is
red-shifted by
0.60 eV from
solution
Fluorescence
* Minimal
fluorescence
broadening due
to aggregation
* Fluorescence
lifetime is longer
in thin films

19. Thin Film Excitation Fluorescence
* Fluorescence energy
and shape is not
affected by the change
in excitation energy
* Fluorescence
efficiency increases
when exciting directly
into CT state

20. Exciton Quantum Confinement in Multi Quantum Wells
So and Forrest, Phys. Rev. Lett. 66, 2649 (1991).
Shen and Forrest, Phys. Rev. B 55, (1997).
Exciton radius = 13 Å

21. (a)
Delocalized CT Exciton
(b)
Localized CT Exciton

22. Electronic Processes in Molecules

23. Effect of Dopants on the Luminescence Spectrum

24. Nonradiative Energy Transfer
How does an exciton in the host transfer to the dopant?
Energy transfer processes:
Radiative transfer
2. Förster transfer
3. Dexter transfer